现代化工

现代化工 ›› 2025, Vol. 45 ›› Issue (11) : 197-202. DOI: 10.16606/j.cnki.issn0253-4320.2025.11.033

科研与开发

磺化聚苯并咪唑/双官能化氧化石墨烯质子交换膜的制备与表征

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Preparation and characterization of sulfonated polybenzimidazole/dually functionalized graphene oxide proton exchange membranes

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文章历史 +

Received		Published
2025-02-14		2025-11-20
Issue Date	Revised Date
2025-11-17	2025-02-14

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摘要

为增强磺化聚苯并咪唑(SPBI)质子交换膜的质子电导率和机械性能,通过原位聚合法将接枝磺酸基团与膦酸基团的氧化石墨烯(SPGO)引入SPBI基体中,制备了不同SPGO含量的SPBI/SPGO高温质子交换复合膜。实验结果表明,SPBI/SPGO质子交换膜断面呈现空间网状结构,SPBI/SPGO复合膜与SPBI膜具有同样优异的热稳定性,SPGO的掺杂提高了复合膜的机械性能,SPBI/SPGO复合膜的拉伸强度最高达到60.0 MPa,是Nafion117膜(26.6 MPa)的2.3倍。SPBI/SPGO-1%质子交换膜表现出良好的尺寸稳定性,酸溶胀度为5%,且在160℃无水条件下质子电导率达到了0.078 S/cm,SPGO的掺杂构建了更多的质子传递通道,促进了高温下SPBI/SPGO复合膜的质子传导。

Abstract

To enhance the proton conductivity and mechanical properties of sulfonated polybenzimidazole (SPBI) proton exchange membranes,graphene oxide grafted with sulfonic acid groups and phosphonic acid groups (SPGO) enters into SPBI matrix through in-situ polymerization,and SPBI/SPGO high-temperature proton exchange composite membranes with different SPGO contents are prepared.Experimental results show that the cross-section of SPBI/SPGO membranes presents a spatial network structure.SPBI/SPGO membranes have the same excellent thermal stability as SPBI membranes.The doping of SPGO brings about an improvement in the mechanical properties of SPBI/SPGO composite membranes.Specifically,SPBI/SPGO composite membranes exhibit a tensile strength of 60.0 MPa,which is 2.3 times that (26.6 MPa) of Nafion117 membranes.SPBI/SPGO-1% proton exchange membranes exhibit good dimensional stability with an acid swelling ratio of 5%.Moreover,their proton conductivity reaches 0.078 S/cm under anhydrous conditions at 160℃.The doping of SPGO constructs more proton transfer channels and promotes the proton conduction of SPBI/SPGO proton exchange composite membranes at high temperature.

Graphical abstract

关键词

磺化聚苯并咪唑 / 质子交换膜 / 质子电导率 / 原位聚合法 / 氧化石墨烯

Key words

sulfonated polybenzimidazole / proton exchange membrane / proton conductivity / in-situ polymerization / graphene oxide

Author summay

王宇豪(2000-),男,硕士生,研究方向为质子交换膜材料,Yuhao.Wang@tuv.com

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language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=Jiangsu Provincial Key Laboratory of Fine Petrochemical Engineering, School of Petrochemical Engineering, Changzhou University, Changzhou 213164, China), AuthorCompanyExt(id=1241417140709847877, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240720215270453303, companyId=1241417140701459267, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=常州大学石油化工学院, 精细石油化工江苏省重点实验室, 江苏常州 4)])])] 王宇豪,张琪,张奎. 磺化聚苯并咪唑/双官能化氧化石墨烯质子交换膜的制备与表征[J]. 现代化工, 2025, 45(11): 197-202 DOI:10.16606/j.cnki.issn0253-4320.2025.11.033

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质子交换膜燃料电池(PEMFC)在众多领域具有广阔的应用前景,通过提升PEMFC的工作温度能够解决CO毒害催化剂的问题,降低燃料的纯度要求,也能简化PEMFC的水热管理^[1]。目前商业化的质子交换膜(PEM)是以Nafion膜为代表的全氟磺酸膜,其质子传导对环境的温度和湿度要求高,一旦燃料电池操作温度高于100℃,全氟磺酸膜会因高温下失水导致质子电导率大幅降低^[2],并且该膜的制备工艺复杂价格昂贵,限制了PEMFC的进一步发展。因此,开发性能优异且更经济的新型质子交换膜势在必行。

聚苯并咪唑(PBI)展现出优良的热稳定性,能够满足燃料电池的运行需求,在磷酸(PA)掺杂后能够在高温低湿度条件下保持优异的质子传导性能^[3-4]。但过量的磷酸掺杂也会导致PA在PEMFC运行过程中流失^[5]。磺化聚苯并咪唑(SPBI)的磺酸基可以增加额外的质子供体,提高膜的质子电导率,从而降低质子传导对PA的依赖^[6],但过高的磺化度也会引起SPBI易溶胀和机械强度降低的问题。氧化石墨烯(GO)亲水性官能团丰富,比表面积较高,能够为磷酸提供吸附位点,抑制PA流失,并形成氢键对质子传输起促进作用,其本身优异的机械性能也有助于提升复合膜的拉伸强度。但GO颗粒在有机溶剂中分散较为困难,通过官能团改性能够改善GO与聚合物的相容性^[7]。磺酸、膦酸基团具有优异的质子传导性能,尤其是膦酸基团,即使在高温无水状态下也能够自电离,为PEM提供可观的质子电导率。因此对GO进行磺酸、膦酸官能化改性不仅能改善GO与SPBI的相容性,也增加了PEM中的质子传递位点,从而构建高效的质子传递通道,提升膜的质子电导率^[8-9]。

本研究将磺酸基与膦酸基接枝到GO上制备双官能化改性的SPGO,并通过原位聚合法将SPGO引入SPBI基质中,通过精确控制SPGO的添加量制备了一系列不同SPGO含量的SPBI/SPGO复合膜。重点考察SPGO含量对复合膜微观形貌、热稳定性、酸掺杂率、尺寸稳定性、高温无水条件下质子电导率以及机械性能的影响,通过计算SPBI/SPGO质子交换复合膜在高温无水条件下的活化能来研究质子传递机理。

1 实验部分

1.1 实验药品

五氧化二磷、亚磷酸、二甲基亚砜(DMSO)、2-甲酰苯磺酸钠购于上海凌峰化学试剂有限公司;5-羟基间苯二甲酸、3,3'-二氨基联苯胺(DAB)、间苯二甲酸-5-磺酸钠(5-SSIPN)、4,4'-二羧酸二苯醚(OBBA)购于阿拉丁(上海)有限公司;无水碳酸钠、三乙烯四胺(TETA)购于江苏强盛功能化学有限公司;过硫酸钾、多聚磷酸(PPA)、无水乙醇、N,N'-二环己基碳酰亚胺(DCC)、高锰酸钾购于国药集团化学试剂有限公司;浓硫酸、乙酸、30%双氧水购于常州恒光化学试剂有限公司,采用改进Hummers法制备GO^[10]。

1.2 SPGO的制备

SPGO的合成路线如图1所示,在三口烧瓶中加入氧化石墨烯和无水乙醇,超声3 h,然后加入适量TETA,超声0.5 h,加入DCC,再超声0.5 h。在60℃的恒温油浴锅中,回流搅拌反应24 h。完成反应后,混合溶液再超声0.5 h,并用聚四氟乙烯膜抽滤,乙醇/去离子水洗涤。将产品在70℃干燥箱中烘干至恒重,得到胺基化的氧化石墨烯GO-TETA。将2-甲酰苯磺酸钠、GO-TETA和乙酸加入亚磷酸中,加热至80℃并在搅拌状态下保持6 h。将反应后溶液进行离心,对所得沉淀反复抽滤洗涤后60℃烘干,得到SPGO。

1.3 SPBI及SPBI/SPGO质子交换复合膜的制备

SPBI采用直接缩聚法合成,通过原位聚合制备SPBI/SPGO质子交换膜:在N₂氛围中,将P₂O₅加入PPA中并加热至120℃搅拌至澄清,再加入 SPGO,待搅拌均匀后降温至50℃,加入DAB、OBBA、5-SSIPN和5-羟基间苯二甲酸,在90、130、160、190℃分别反应6、11、3、5 h。将反应物倒入去离子水中,加入Na₂CO₃中和,并水洗至中性,将烘干后的产物溶解于DMSO中得到5%的SPBI/SPGO制膜液,将制膜液在玻璃板上刮涂后烘干,最后将膜浸泡在磷酸中48 h进行磷酸掺杂。质子交换膜命名为SPBI/SPGO-X,其中X为SPGO的质量分数。

1.4 表征与性能测试

傅里叶转换红外光谱使用TENSOR 27红外光谱仪,扫描波长范围为400~4 000 cm^-1;采用共聚焦显微镜拉曼光谱仪(美国Thermo Scientific公司)分析样品的结构;采用ZEISS SUPRA55型扫描电子显微镜(SEM)表征膜的微观形貌;质子交换复合膜的酸掺杂率及酸溶胀度通过干湿称重法测定;热重分析采用NETZSCH TG209F3型热重分析仪以10℃/min的升温速率在N₂氛围内测试样品的热稳定性;使用Instron拉力试验机(WDT-10)在室温下以2 mm/min的拉伸速率测试样品的机械性能,每个样品膜测定3次,取平均值。采用四电极交流阻抗法在0.1~100 kHz范围内测定质子交换膜的质子电导率^[11],并通过Arrhenius方程计算膜的活化能E_a。

2 结果与讨论

2.1 SPGO的红外光谱

图2为GO和SPGO的红外光谱图,3 445 cm^-1处特征峰为—OH振动吸收峰,1 629 cm^-1处特征峰对应于GO中未被氧化的C=C官能团^[12]。与GO相比,SPGO在1 735 cm^-1(—COOH伸缩振动)、1 400 cm^-1(—OH变形振动)和1 228 cm^-1(环氧基伸缩振动)处吸收峰的峰强度减少。1 577 cm^-1处的新特征峰是C—N伸缩振动,1 206 cm^-1处的峰是由于膦酸基团和磺酸基团的相互作用。结果表明,SPGO的修饰是成功的。

2.2 SPGO的拉曼光谱

图3为GO和SPGO的拉曼光谱图。SPGO类似于GO在拉曼光谱中有2个吸收峰,分别位于 1 346、1 586 cm^-1处,分别对应着D峰和G峰,改性后的GO没有改变氧化石墨烯的基本结构。D峰和G峰的峰强度比(I_D/I_G)可作为检测石墨烯无序度的标准^[13],SPGO的强度比I_D/I_G值从GO的1.00增加到改性后1.14。氨基膦酸化的改性引起GO平面内的sp²区域发生变化,导致GO平面结构的弯曲变形,同时破坏了GO的对称结构,略微扩大了GO的无序性,扩大了GO缺陷结构。因此,I_D/I_G增加反映了新缺陷或边缘的出现,这为成功实现GO的功能化改性提供了直接证据。

2.3 SPBI/SPGO质子交换膜的红外光谱

图4为SPBI/SPGO质子交换膜的红外光谱图。由图可知SPBI/SPGO与SPBI具有相似的特征峰。其中磺酸基团的伸缩振动峰出现在951、1 043、1 114 cm^-1处。相较于SPBI膜,SPBI/SPGO复合膜在1 176 cm^-1处的特征峰有所增强,这是由于膦酸基团的作用。苯环对应的特征峰出现在1 460 cm^-1附近。而1 600 cm^-1附近的特征峰是由C=N键的伸缩振动引起。

2.4 SPBI/SPGO质子交换膜的微观形貌

图5显示了SPBI膜和SPBI/SPGO复合膜断面的微观形貌。从图中可以看出,SPGO纳米片很好地分散在SPBI基质中。SPBI膜和SPBI/SPGO复合膜的断面都呈现交织的空间网状结构,并且复合膜的网状结构比SPBI膜更密集和明显。SPBI/SPGO膜的网络结构有助于改善膜的机械性能。

2.5 SPBI/SPGO质子交换膜的酸掺杂率和酸溶胀度

表1为SPBI/SPGO质子交换膜的酸掺杂率与酸溶胀度。从表1可以看出,SPBI/SPGO复合膜的酸掺杂率低于SPBI膜,SPGO的加入降低了膜内聚合物链的流动性和自由体积,一定程度上抑制了磷酸在质子交换膜中的渗透。随着SPGO含量的增加,SPBI/SPGO复合膜的酸掺杂率不断增加而酸溶胀度不断减少,这是由于SPGO中的氮元素存在孤电子对,会吸引质子形成胺基正离子,为磷酸提供了吸附位点,可以锁住更多的酸,抑制酸损失。同时SPGO存在储酸的空间,在酸溶胀过程中通过空间立体效应抑制了SPBI主链的运动^[14],使得SPBI/SPGO复合膜的酸掺杂率增加,溶胀度降低,提高了复合膜的尺寸稳定性。

2.6 SPBI/SPGO质子交换膜的热稳定性

图6为SPBI/SPGO质子交换膜的热重曲线,热损失分为3个阶段:在200℃以内的轻微失重是由于水和残留溶剂的挥发;在300~500℃的失重是由于SPBI与SPGO含氧酸发生了分解;500℃以后的失重归因于SPBI聚合物主链的分解。从图中得知SPGO的掺杂对质子交换膜的热稳定性影响很小,SPBI/SPGO质子交换复合膜的热稳定性能够满足燃料电池在高温下操作的需要。

2.7 SPBI/SPGO质子交换膜的机械性能

表2显示了SPBI和SPBI/SPGO质子交换膜的机械性能。相较于SPBI膜,SPBI/SPGO复合膜具有更高的拉伸强度,最大达到60.0 MPa,比Nafion117膜^[15](26.6 MPa)高出2.3倍。SPGO本身有着出色的力学性能,使得复合膜拥有更大的拉伸强度,并与SPBI形成网状结构,提升了复合模的柔韧性,使得SPBI/SPGO复合膜的断裂伸长率得到提升。同时,SPGO的磺酸和膦酸基团与SPBI的咪唑基团能够形成氢键,这也有助于提升复合膜的力学性能,并且优异的机械性能有助于提升燃料电池的使用寿命^[16]。

2.8 SPBI/SPGO质子交换膜的质子电导率

质子电导率作为质子交换膜的核心指标,直接反映了质子交换膜的质子传导性能,图7显示了SPBI和SPBI/SPGO质子交换膜在80~160℃范围内无水条件下的质子电导率,随着温度的上升,磷酸的质子解离能力提升,质子跳跃速率加快,SPBI/SPGO复合膜的质子电导率也随之升高。SPBI/SPGO复合膜较SPBI膜表现出更高的质子电导率,SPBI/SPGO-1%复合膜表现出最高的质子电导率,在160℃无水条件下达到0.078 S/cm,是相同条件下SPBI膜的2.3倍。这是因为SPGO具有较大的比表面积,SPGO纳米颗粒上接枝的含氧酸基团与SPBI中的咪唑基团和酚羟基之间形成氢键网络:—SO₃H┄H₂O₃P—、—SO₃H(或—PO₃H₂)┄HO—、—SO₃H(或—PO₃H₂)┄HN—,氢键网络为质子传递提供了有效的路径。SPBI中含有大量的醚键与咪唑类的含氮杂环,在高温无水条件下可促进含氧酸基团的电离,增加质子的流动速度,加快氢键网络的断裂-结合的速率^[17-19]。此外,磷酸可以促进氢键的形成,作为一种两性酸,既是质子供体又是质子受体,缩短了质子跳跃位点之间的距离,在高温无水条件下,磺酸基团与膦酸(磷酸)基团失水形成酸酐SO₂—O—SO₂、(HO)PO—O—PO(OH)、SO₂—O—PO(OH),但(HO)PO—O—PO(OH)与SO₂—O—PO(OH)中存在的P—OH基团比未缩合的P—OH基团具有更强的酸特性^[20],其中SO₂—O—PO(OH)中存在的P—OH最为明显,使得膦酸(磷酸)基团更容易电离。因此膦酸基团、磺酸基团与酚羟基通过协同作用构建了超快速质子传递通道,从而改善SPBI/SPGO复合膜的质子电导率。

图8是SPBI膜和SPBI/SPGO-1%复合膜的阿伦尼乌斯曲线。从图中可以看出,SPBI膜的E_a值为24.30 kJ/mol,SPBI/SPGO-1%复合膜具有较低的活化能,E_a值为22.32 kJ/mol,说明复合膜需要较低的活化能就能在邻近的分子或质子缺位间跳跃。SPGO/SPBI-1%复合膜较低的E_a值与较高的质子电导率证实了SPGO的掺杂减少了质子迁移阻碍并为质子快速传导提供有效途径。

3 结论

通过对GO进行双官能化改性合成接枝磺酸基团与膦酸基团的SPGO,利用原位聚合法成功制备了不同掺杂比例的SPBI/SPGO质子交换复合膜。SPGO的加入大大提高了复合膜机械强度,明显高于SPBI膜和Nafion膜。复合膜的拉伸强度最大可达到60.0 MPa,为Nafion膜的2.3倍。SPBI/SPGO复合膜的热稳定性优异,满足高温下运行的条件。SPBI/SPGO-1%质子交换膜的酸掺杂率达到197.5%,而酸溶胀度为5%,表现出良好的含酸率与尺寸稳定性。SPBI/SPGO膜在高温无水条件下具有良好的质子传导性能,并且随着SPGO掺杂量的增加而升高,SPBI/SPGO-1%复合膜的质子电导率在160℃无水条件下达到了0.078 S/cm。这些结果表明,SPBI/SPGO质子交换复合膜在高温PEMFC中具有广阔的应用前景。

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